3-acylamido-5-pyrazolone and 3-acylamido-5-acyloxypyrazole couplers for color photography



S-ACYLAMIDO-S-PYRAZOLONE AND S-ACYL- AMIDO-S-ACYLOXYPYRAZOLE COUPLERS FOR COLOR PHOTOGRAPHY 7 George Feniak, Anthony Loria, and Warren A. Reckhow,

Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y.,a corporation of New Jersey Application October 30, 1956, Serial No. 619,151

' 7 Claims. (CI. 96-55) This invention relates to 3-acylamiclo-5-pyrazolone and 3-acylamido-5-acyloxypyrazole couplers for color photography and more particularly to those pyrazolones and pyrazoles having hydroxyalkyl and acyloxyalkyl groups in the l-poSitiOn.

3-acylamido-5.-pyrazolone couplers for color photography have previously been described and more particularly certain 1 alkyl 3 acylamido pyrazolone couplers. Similarly, certain S-acyloxy pyrazole couplers have previously been described. However, the couplers of the present invention are distinct in having the l-hydroxyalkyl or l-acyloxyalkyl substituents which confer special properties upon the dyes obtained therefrom in,

wherein R represents a member of the class consisting of; a hydrogen atom and a carboxylic acid acyl group such as a phenoxyacetyl', heptoyl, benzoyl'groupgetc Ry and R each represent a carboxylic acid acyl group such as a phenoxyacetyl, lauroyl, tetracosyl, benzoyl, palmitoyl, heptoyl group, etc., and R represents a hydrogen atom, and alkyl group preferably containing from 1 to 4 carbon atoms e. g. methyl, ethyl, n-propyl'and n-butyl, or a monocyclic aryl group of the benzene series such as phenyl. and nuclear-substituted phenyl.

Representative couplers having these structures are as follows:

I. l-(fl-hydroxyethyl) 3 [a-(p-palmitamidophenoxy)- acetamido]-5-pyrazolone LI [a (2. di n y p o y xy)ethy l: 3 (2,4 di n amylphenoxyacetamido) 5 y phen y cetoxy) -py. a..zole. III. 1 phenoxyacetamido)-5 (octanoyloxy)-pyrazole v United States Patent IV. 1 (,3 phenylacetoxyethyl) '3 (2,4 di n amylphenoXyacetamido) -5-(phenylacetoxy)-pyrazole V. l (,6 hydroxyethyl) 3 (2,4 di n amylphenoxy)acetamido-S-pyrazolone VI. 1 (,8 phenoxyacetoxyethyl) 3 (2,4 di namylphenoxyacetamido) 5 (phenoxyacetoxy)- pyrazole 7 VII. l'- (,8 hydroxyethyl) 3- {p [In (2,4 di-' tert amylphenoxyacetamido)benzamido]phenoxyacetamido}-5-pyrazolone VIII. 1 [e (2,4 di tert -amylphenoxyacetoxy) ethyl]- 3 (2,4 di tert amylphenoxyacetamido) 5-; (2,4 di tert amylphenoxyacetoxy) pyrazole IX. 1 (5 phenyl ,8 hydroxyethyl) 3 (p nitro-. phenoxyacetamido)-5-pyrazolone X. 1 (p hydroxypropyl) 3 (p nitrophenoxyacetamido)-5-pyrazolone XI. 1 (,8 hydroxyethyl) 3 [a (2,4 di -tert amylphenoxy) acetamido]-5-pyrazolone XII. l (p hydroxyethyl) 3 lauramido 5 pyrazolone XIII. 1 (B benzoyloxyethyl) 3 benzamido 5- pyrazolone XIV. 1 (5 hydroxypropyl) 3 [4 (2,4 di tert amylphenoxyacetamido.)phenoxyacetamido] 5- pyrazolone XV. 1 3 hydroryethyl) 3 tetracosanamido ii (,3 octanoyloxyethyl) 3 (2,4 di n amyl' pyrazolone XVI. 1 (B hydroxyethyl'). 3, (p

acetamido)-5-pyrazolone I XVII. 1 (B hydroXyethyl) 3 i-pyrazolone nitrophenoxy- (m nitrobenzamido)- The benzoylacet-o-alkoxyanilide couplers with which the couplers of the present invention are particularly" useful are described in the McCrossen et al. U. S. patent application Serial No. 575,099, filed March 30, 1956, and have the following general formula:

ooomoorrn-@ 6R. wherein R represents an alkyl group of from about. 110.- 20 carbon atoms and one of the groups X. and: Y rep resents a hydrogen atom and the other represents; an. organic acid acylamido group. t 1 1, A particular group of these benzoylacet-o-alko)kyanilide couplers elficacious for use with the above couplers of the lnvention have the above general formula wherein R represents an alkyl group of from'about 1 to 20 carbon atoms and one of the groups X and Y represents a hydrogen atom and the other represents the group.

7 R p g -NHC o (1114)- can CrHn I wherein R alkyl group of from about 1 to 4 carbon atoms.

benzoyl}-2-methoxyacetanilide represents either a hydrogen atom or an couplers} The reason why the couplers of the invention are particularly useful with the benzoylacet-o-alkoxyanilide couplers above will be apparent from consideration of thespectral absorption curves shown in the drawing. Curve '1 of Fig. 1 illustrates the region of light absorption of the lemon-yellow dyes'obtained in color development of the -benzoylacet=O-alkoxyanilide couplers with a particular primary aromatic amino silver halide developing a gent.-

Curve 2 illustrates the region of absorption of a similar methoxy (2',4' di -tertdye made by coupling the same color developing agent i with a typical l-alkyl 3 acylamido-S-pyrazolone coupler 1-methyl-3- [4-(2,4-di-tert.-amylphenoxyacetamido phenoxybutyramido) -5-pyrazolone Curve 3 illustrates the region of absorption of a similar dye made from the same color developing agent and one of the couplers of the invention (Coupler No. NII).

Curve 4 illustrates the region of absorption of a dye made from typical known magenta coupler 1-(2,4,6-trichlorophenyl) -3-[ 3 (2,4-di-tert-amylphenoxyacetamido) benzamidol] 5 -pyrazolone (U. S. 2,600,788) using the same developing.

It will be noted from these curves that a rather large gap in absorption appears between curve 1 and curve 4 rated when the. reaction mixture was cooled. Twenty g. of this material was treated with 10 ml. of aq. sodium hydroxide in 400 ml. of ethanol. The reaction mixture was warmed to 65 C. for ca. 15 min. The mixture was filtered, the filtrate was acidified with glacial acetic acid and cooled. The solid was recrystallized from a mixture of dimethylformamideacetonitrile and washed with ether (M. P. 182-184 C.).

Calc. for O20 4e 40s Percent COUPLER II 1 Q [fl-(2,4-di-nfimylphnoxyacetoxy)ethyl]-3-(2,4-di-n amylphenoxyacetamido) 1 5 (2,4-di-n-amylphenoxyacetoxy) -pyraz0le A mixture of 2.84 g. of l-(B-hydroxyethyl)-3-amino- 5- pyrazolone, 100 ml. of dry acetonitrile, 18.7 g. of 2,4- di-n-amylphenoxyacetyl chloride and 7.3 g. of N,N-dif methylaniline was stirred'and heated to reflux for 3 hours. The mixture was drowned out in water and the product in the region of wavelength 500 millimicrons which is undesirable because when these dyes are employed together in a subtractive color system, the result is that the yellow colors are reproduced as colors which are more green than desired. Considering curve 2, the absorption maximum is shifted in the right direction but the dye is too sharp-cutting (does not have a wide enough range of absorption). However, when the couplers of the invention (curve 3) are employed with the benzoylacet-oalkoxyanilide couplers, due to the wider range of light absorption of the dyes obtained from the couplers, the gap in absorption between the yellow and magenta dyes is-closed sufficiently resulting in more faithful reproduction of the colors.

' The couplers of the invention may be prepared in the following manner:

COUPLER I I-(B-hydroxyethyl) -3-lu-(p-palmitamidophenoxy)-acetamido] -5-pyrazo'lon.e

l-(fi-hydroxyethyl) 3 (p-nitrophenoxyacetamido)- S-pyrazolone was prepared in the same manner as was 1 (B-phenyl-p-hydroxyethyl) 3 (p-nitrophenoxyacetamido)-5-pyrazolone.IX except that l-(B-hy'droxyethyD- 3-amino-5-pyrazolone was used in place of l-(fl-phenylp-hydroxyethyl) 3 amino-S-pyrazolone. This material was reducedin glacial acetic acid, over 10%. palladium on charcoal at ca. C. with hydrogen at a pressure of ca. 30 lbs. per sq. in.. The catalyst was filtered off, the filtrate was concentrated and the residue was treated with 3 equivalents of palmitoyl chloride, in refluxing acetoni trite, in the presence of 3 equivalents of N,N-dimethylaniline, for 90 minutes. The triacylated material sepawas recrystallized from ethanol (M. P. 61-63").

Cale. for CnHM aOA Percen COUPLER III I-(B-octanoyloxyethyl) 3 (2,4-di-n-amylphenoxy-acetamide) -5- (octanoyloxy pyrazole Coupler II was hydrolyzed with two equivalents of sodium hydroxide in aqueous ethanol in the usual manner. The resulting l-(fl-hydroxyethyl)-3-(2,4-di-n-amylphenoxy acetamido)-5-pyrazolone melted at 143-144". This material was acylated with two equivalents ot octanoyl chloride, in the presence of 2 equivalents of N,N-dimethylaniline in dry acetonitrile. The product, after recrystallization from methanol, melted at -2" C.

Anal. Calc. for

czs ar aoi Found Percent Percent 70. 6, 70. 3 9. 9

COUPLER IV 1 (B-phenylacetoxyethyl)-3-(2,4-di-n-amylphenoxy-acetamido) -5- (phenylacetoxy pyrazole This compound was prepared in the same manner as was Coupler III except that phenylacetyl chloride was used in place of octanoyl chloride. It melts at 72-3".

Anal. Calc. for

i Found I OsgHflNSOG Percen Percent COUPLER V l-(fi-hydroxyethyl) -3-(2,4-di-n-amylphenoxy)acetamido- S-pyrazolone This compound was prepared in the same manner as was coupler XI below except that 2,4-di-n-amylphenoxyacetyl chloride was used in place of 2,4-di-tert-amylphenoxyacetyl chloride. It melted at 143-144 C.

Anal. Calc. for Found 2sH4sNa04 Percent Percent C 66. 3 66. 2, 66. 6 H 8. 5 8. 8. 4 N l0. 2 10. 1

COUPLER VI 1- (B-phenoxyacetoxyethyl) -3(2,4-a'i-n-amylphenoxyacetamido -5- (phenoxyacetoxy pyrazole This couple was prepared in the same manner as was Coupler IV except that phenoxyacetyl chloride was used as the acylating agent. The product melts at 89.5-9l.

1 (,8 hydroxyethyl) 3 {p [m (2,4 di tert amylphenoxyacetamido) benzamido]phenoxyacetamido} 5- pyrazolone A mixture of 18.5 g. of 1-(fi-hydroxyethyl-3-(p-nitrophenoxyacetamido)-5-pyrazolone (above), 50 ml. of dry acetonitrile, 17.5 g. of benzoyl chloride and 16.6 g. of N,N-dimethylaniline was heated to reflux overnight. The reaction mixture was drowned out in water and the product recrystallized from acetonitrile. Five g. of this material was reduced in tetrahydrofuran, at room temperature, over 10% palladium on charcoal and hydrogen at a pressure of ca. 40 lbs. per sq. in. The catalyst was filtered oif and the filtrate was concentrated. The residue was taken up in 50 ml. of dry acetonitrile and treated with 4.1 g. of m-(2,4-di-tert-amylphenoxyacetarnido)benzoyl chloride and 1.2 g. of N,N-dimcthylaniline. The reaction mixture was refluxed overnight. On cooling, the triacylated compound separated from solution. This was recrystallized from acetonitrile. A mixture of 5 g. of this material, 50 ml. of ethanol, and 8 ml. of 2.5 N aq. sodium hydroxide was refluxed for 30 min, cooled, and acidified with glacial acetic acid. The solid that separated was slurried in boiling acetonitrile and recrystallized from ethanol (M. P. 156-163 C.).

1 [5.- (2,4 dz tert amylphenoxyacetvxy)ethyl] 3- (Z,4 di tert amylphenoxyacetamido) 5 (2,4-

di-tert-amylphenoxyacetoxy)-pyraz0le This coupler was prepared in the same manner as was {Coupler 11 except that 2,4-di tert amylphenoxyacetyl chloride was used in place of 2,4-di-n-amylphenoxyacety1 chloride. It melted at 113-116".

Anal. Calc. for Found Cn srN'aOs Percent Percent O 73. 3 73. 1 9. 2 8. 6 4. 3 4.2

COUPLER IX .Z-([B-phenyl-B-hydroxyethyl) 3 (p-nitrophenoxyacetamido )-5-pyraz0l0ne Anal. Calc. for Found ClQHlsNtOfl 7 Percent Percent O 57.3 57.9 H 4.6' 4.9 N 14.1 14.5

COUPLER X I-(B-hyaroxypropyl) 3 (p-nitrophenoxyacetamido)-5- pyrazolone 1-(18-hydroxypropyl) 3 amino-S-pyrazolone was prepared by the method used in the preparation of l-(B- hydroxyethyl) 3 amino-S-pyrazolone except that p-hydroxypropylhydrazine (I. Am. Chem. Soc. 76, 1283, (1954), was used in place of B-hydroxyethylhydrazine. The product was acylated with p-nitrophenoxyacetyl chloride by the method used in the acylation of l-(B-hydroxy-B-phenylethyl)-3-amino-5-pyrazolone. The prod uct was recrystallized from butanol (M. P. 255-6).

Anal. Calc. for Found CitHmNtOa Percent Percent C 50. 0 50. 3 4. 8 5. 0 16. 7 17.0

(0.3 mole), and dimethylaniline, 36.3 g. (0.3 mole), were heated in 500 ml. of dry acetonitrile at reflux overnight. The next morning the reaction mixture containing the triacylated pyrazolone was poured into 2.5 l. of cold water and the oil that separated was washed several times with water by decantation.

The oil layer was then taken up in 500 ml. of 3A alcohol containing 16.8 g. of potassium hydroxide and allowed to stand two hours at room temperature. The mixture was acidified by the addition of 20 ml. of acetic acid contained in ml. of water, and the solid which precipitated was filtered, washed well with water, and air dried.

The product was crystallized from toluene twice, getting white needles melting between -106 C.

Anal. Calc. for Found Csa asNss(401) Percent Percent 1 -(;3-hydroxyethyl) -3-amino-5-pyrazolone obtained which gave the following chemical analysis:

Anal. Calc. for Found C5HtNsO2(l43) Percent Percent COUPLER XII 1-(fl-hydroxyethyl)-3-lauramide-S-pyrazolone This compound was prepared in the same manner as was 1 (fi-hydroxyethyD-B [a-(2,4-di-tert-amylphenoxy) acetamidol-S-pyrazolone XI except that lauroyl chloride was used as the acid chloride. It was recrystallized from ethyl alcohol and melted at 112-115 C.

Anal. Calc. for Found CmHnNsOs Percent Percent C 66. 0 66. 2 H 10. 2 10. 4 N 11. 0 10. 8

COUPLER XIII 1 p-benzoyloxyethyl -benzamido-5-pyrazolone Anal. Calc. for Found CnHnNrOe Percent Percent C 65. 4 65. 1 H 5. 1 4. 8 N 12. 5 12.0

COUPLER XIV This compound is prepared from Coupler X by reduction of the nitro group and reaction with 2,4-di-tertamylphenoxyacetyl chloride.

COUPLER XV 1 (fl-h yd roxyeth yl -3-tetracosanamid0-5-pyraz0lone This compound was prepared by the same method used for .preparing l-(fl-hydroxyethyl)-3-[a-(2,4-di-tertamylphenoxy)acetamido]-5-pyrazolone XI. It too was s crystallized from toluene and had a melting point between 167-169" C.

Anal Calc. for Found C2sHssN3Os(493) Percent Percent The coupler compounds of the invention find usage in a wide variety of photographic color processes wherein silver halide emulsions are developed in the presence of the couplers. For example, Couplers Nos. IX, X, XIII, XVI, XVII, XVIII are most useful in color developing solutions for the development of multilayer color films in which some or all of the emulsion layers are devoid of coupler compounds. A typical color developing solution in which such couplers can be incorporated is as follows:

G. 2-amino-5diethylaminotoluene sulfate 2.5 Sodium sulfite (anhydrous) 5 Sodium carbonate (anhydrous) 20 Potassium bromide 2 Water to 1000 cc.

The couplers can be incorporated into the developer compositions by first dissolving them in a solvent such as isopropyl alcohol and adding this solution to an alkaline developer composition. About 3 grams of the couplers of the invention are suitable for use in developer compositions such as the above.

Color developing solutions thus containing the couplers of the invention are used in well known subtractive color processes. A color film containing at least one emulsion layer and preferably two or three emulsion layers sensitized to different regions of the spectrum is exposed to a subject, developed in a black-and-white developer followed by selective reversal exposure and the exposed emulsion layer color developed with the above developing solution containing one of the coupler compounds appropriate for the particular emulsion layer which has been reversal exposed.

The other couplers which are substantially nondifiusing in emulsion layers such as gelatino silver halide emulsion layers are most appropriate for use in silver halide emulsion layers designed for color processes of the well known negative-positive and reversal types. These less ditfusible couplers, for example, Couplers Nos. I-VIII and XI-XV can be dispersed in an emulsion layer such as a gelatino silver halide emulsion layer by means of coupler solvents including cellulose esters, natural and synthetic resins and organic crystalloidal materials having a boiling point above about 170 C., as described in the Marines etal. U. S. Patent 2,304,940, granted December 15, 1942, and the Jelleyat al. U. S. Patent 2,322,027, granted June 15, 1943. The optimum quantity of coupler to use in the emulsion layer (as in the case of use in a color developer) can be determined by simple experiment and will depend somewhat upon the coupling activity of the particular coupler, the silver halide content of the emulsion layer, the particular process in which the emulsion is to be used and other factors well known in the art of emulsion making.

A typical procedure for making an emulsion and color film therefrom is as follows:

Six-tenths gram of l-[B-(2,4-di-n-amylphenoxyacetoxy)ethyl] 3 (2,4 di n amylphenoxyacetamido)-5- (2,4-di-n-amylphenoxyacetoxy)-pyrazole (Coupler II) was dissolved in 1.2 g. of tricresylphosphate by heating to C. with stirring. This solution was mixed with 17.7 ml. of 10% gelatin solution containing 2 ml. of 5% Alkanol B. The mixture was passed through a colloid mill four times to disperse the coupler solution.

up to a total of 40 g. with additional water.

Fourteen ml. of water used to rinse out the colloid mill was added to the dispersion, which was then made This dispersion was mixed at 40 C. with 8.5 ml. of a melted sensitive silver bromoiodide emulsion of the type described byTrivelli and Smith in the Phot. Jour. Vol. 79, pp. 33041, (1939), and the mixture was coated on a cellulose acetate support. After drying, the coating was exposed under an image and developed in a 2amino- S-diethylaminotoluene developing composition to form a silver and magenta dye negative image. The silver image and residual silver halide were removed with ferricyanide-hypo bleach leaving a negative image having maximum absorption at a wavelength of 528 me.

The couplers of the invention can be employed in a multilayer color film in conjunction with the benzoylaceto-alkoxyanilide couplers for the purposes mentioned as follows: A multilayer film was prepared using emulsion melts made in a manner similar to that described in the single layer example above: (1) a gelatin dispersion of a cyan coupler, l-hydroxy-Z-[6(2,4-di-tert.amylphenoxy)- n-butyll -naphthamide dissolved in tricresylphosphate was added to a red-sensitive gelatin silver-halide emulsion and coated as the bottom layer, (2) a gelatin dispersion of a magenta coupler, I-Efl-(ZA-di-n-amylphenoxyacetoxy) ethyl] 3 (2,4 di n amylphenoxyacetamido) 5 (2,4 di namylphenoxyacetoxy) parazole (Coupler II), dissolved in tricresyl phosphate was.

added to a green-sensitive gelatin silver-halide emulsion and coated as the middle layer, and (3) a gelatin dispersion of a yellow coupler, t"{3-[DC-(2,4-di-tCI'L-3IHYL phenoxy) acetamidolbenzoyl} 2 methoxyacetanilide dissolved in di-n-butylphthalate, was added to an unsensitized gelatin silver-halide emulsion and coated as the top sensitive layer over a Carey Lea silver yellow filter interlayer. The film was exposed and processed as in the same manner as the single layer material above.

A multilayer color film prepared as just described is illustrated in Fig. 2 in the drawings wherein layer 20 represents a support such as a cellulose ester film base, layer 21 represents a red-sensitive silver halide emulsion layer containing a cyan coupler, layer 22 represents a green-sensitive silver halide emulsion layer containing the coupler compound of the invention, layer 23 represents a yellow filter layer such as a Carey-Lea silver filter layer and layer 24 represents a blue-sensitive silver halide emulsion layer containing the mentioned benzoylacet-o-alkoxyanilide coupler. Such a film can be developed directly to a color negative or indirectly to a color positive by well known reversal methods.

The 3-acylamido-S-acyloxypyrazole couplers of the invention can be used in emulsion or color developing solutions in substantially the same manner as described for the S-pyrazolone couplers of the invention above. These pyrazole couplers are particularly useful in that they have lower melting points and higher solubility in coupler solvents than the corresponding -pyraz'olones,

although the S-pyrazole compounds tend to be somewhat less active couplers. It will be noted from the syntheses of, for example, Couplers VII and XI that the monoacylated couplers are readily obtained by hydrolysis of the triacylated S-pyrazoles disclosed, the 3-acylamido group of the acylated S-pyrazoles being more resistant to hydrolysis.

The color developing agents used for development of emulsion layers in the presence of the novel coupler compounds include the well known primary aromatic amino silver halide developing agents such as the phenylenediamines including the alkyl phenylenediamines and alkyl toluene diamines as well as the p-aminophenols in which the amino group is unsubstituted. The N-alkyl sulfonamido alkyl-p-phenylenediamine developing agents of U. S. Patent 2,193,015 are particularly useful for the development of emulsion layers in the presence of the couplers of the invention.

The silver halide component of the emulsion layers 'is not especially critical and may be, for example, silver bromoiodide, silver bromide or silver chloride, etc., depending upon'the results desired. Likewise, the emulsions which are developed in the presence of the novel couplers may consist of single-layer o1 differentially sensitized multilayer films.

The hydrophilic colloid vehicle of the emulsions may be selected from known types including gelatin, hydrolyzed cellulose esters, polyvinyl alcohol and other natural and synthetic organic colloids.

The examples and compounds set forth in the present specificationare illustrative only and it is to be understood that our invention is to be taken as limited only by the scope of the appended claims.

What we claim is:

l. A photographic silver halide emulsion containing a coupler compound of the class consisting of those having the general formulas I R3 C=CH wherein R represents a carboxylic acid acyl group.

3. A photographic silver halide emulsion containing a compound of the class consisting of 1[ 8-(2,4-di-namylphenoxy acetoxy)ethyl] 3 (2,4 di 11 amylphenoxyacetamido) 5 (2,4 di n amyl acetoxy) pyrazole, 1 (B phenylacetoxyethyl) 3- (2,4 di n amylphenoxyacetamido) 5 (phenylacetoxy) pyrazole, 1 (,8 phenoxyacetoxyethyl) 3- (2,4 di n amylphenoxyacetamido) 5 (phenoxyacetoxy) pyrazole, l (,8 hydroxyethyl) 3 [a- (2,4 di tert amylphenoxy)acetamido] 5 pyrazolone, 1 (p hydroxyethyl) 3 (p nitrophenoxyacetamido)-5-pyrazolone.

4. A multilayer color film comprising a support having thereon a silver halide emulsion designated in claim 1 sensitive to green light and a silver halide emulsion sensitive to blue light containing a coupler compound having the general formula wherein R represents an alkyl group of from 1 to 20 carbon atoms and one of the groups X and Y represents a hydrogen atom and the other represents an organic acid acylamido group.

5. A multilayer color film comprising a support having thereon a silver halide emulsion designated in claim 1 sensitive to green light and a silver halide emulsion sensiphenoxy- 11 tive to blue light containing a coupler compound having the general formula wherein R represents an alkyl group of from 1 to 20 carbon atoms and one of the groups X and Y represents a hydrogen atom and the other represents the group R! NHCO (in-0005B i CsHu wherein R represents a member of the class consisting of a hydrogen atom and an alkyl group of from 1 to 4 car bon atoms.

6. A multilayer color film comprising a support having thereon a silver halide emulsion designated in claim 1 and sensitive to green light, and a silver halide emulsion sensitive to blue light containing a coupler compound of the class consisting of a {3 [1x (2,4 di n amylphenoxy)butyramido] benzoyl}-2-methoxyacetanilide 3 benzoylacetamino 4 methoxy (2',4' di tertamylphenoxy)-acetanilide a-{3- oz- (2,4-di-tert-amylphenoxy) acetamido] -benzoy1}-2- methoxyacelanilide a {3 [a (2,4 di tamylphenoxy)butyramido] ben zoyl}-2-methoxyacetanilide a Benzoyl 5 [at (2,4 di tert. amylphenoxy)butyramido] -2-methoxyacetanilide 12 a {4 [u (2,4 di tert amylphenoxy)acetamido] benzoyl}-2-methoxyacetanilide 4 benzoylacetamido 3 methoxy (2',4 di tertamylphenoxy) -acetanilide 7. A method of producing a colored photographic image in a developable silver halide emulsion layer which comprises developing said layer with a primary aromatic amino silver halide developer in the presence of a coupler compound of the class consisting of those havingthe wherein R represents a member of the class consisting of a hydrogen atom and a carboxylic acid acyl group, R and R each represent a carboxylic acid acyl group and R represents a member of the class consisting of a hydrogen atom, an alkyl group of from 1 to 4 carbon atoms and a monocyclic aryl group of the benzene series.

References Cited in the file of this patent UNITED STATES PATENTS Loria et al. Oct. 25, 1955 Loria et al. Nov. 27, 1956 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION atent No, 2365 748 December 23, 1958 George Feniak et al0 It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3y line 3 "N11" read XII eolumn 1C1 line 339 after 'aeid" insert= aeyl m Signed and sealed this 5th day of May 1959.,

:SEAL) Xt'test:

MEL AXLINE ROBERT (J. WATSON Lttesting Oflicer Commissioner of Patents 

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING A COUPLER COMPOUND OF THE CLASS CONSISTING OF THOSE HAVING THE GENERAL FORMULAS 